Hydrogenation of liquid olefin polymers



Patented Sept. 24, 1940 UNITED STATES PATENT oFFics 3 2,215,876 HYDMGENATION OF LIQUID OLEFIN POLYMERS Paul Herold, Leuna, Walter Kroeni Ludwig!- haten on the Rhine, Hermann Kaufmann, Leuna, and Ernst Donath, Mannheim, Germany, aseignors to Standard-L G. Company, Linden, N. 1., a corporation of Delaware N 0 Drawing.

Application June 9, 108%, Serial No.

212,804 In Germany June 11, 1937 tain sulphides molybdenum and/or tungsten (component a) together with sulphides of nickel and/or cobalt (component b). Mixtures comprising sulphides of tungsten and nickel are preierred.

The sulphides of molybdenum and/or of tungsten are employed together with those of nickel and/or of cobalt in various proportions. As a rule, between i and 3 molecular proportions of component a are present for between 3 and 7 molecular proportions of component b, preferably between 3 and 1 molecular proportions oi component a ior 1 molecular proportion of component b.

as a rule, in practice the catalyst consists substantially entirely oi the said components. However, where desirable other catalytically active substances or promoters such as alumina, magnesia, maauesium carbonate and, in particular, other sulphides, such as zinc sulphide, vanadium ill sulphide or iron sulphide, or carrier substances such as diatomaceous earth, bleaching earths and the like can be added.

llhe components oi the catalyst are preferably employed in a state of intimate mixture with one an another and any suitable method for preparing the said mixed catalysts may be employed, for example, the methods ior the production of xed catalysts described in the British Pat ent No. 447,407 or similar methods. as The hydrogenation is, as a rule, carried out at temperatures of 150 to 350 0., in particular between 175 and 275 0., and under a pressure oi more than 20 atmospheres, advantageously about 50 atmospheres, for example of about 100,

d0 200, 250 atmospheres or more, with an excess of octenes into mixed octancs or for the conversion of tri-isobutene into the corresponding saturated hydrocarbons. if desired, together with the liquid olehnes of the gasoline range to be hydroserrated, other liquid hydrocarbons may also be present. The products obtained may be employed with particular advantage as motor fuels of high octane nber.

The present invention is attended by numerous advantages. In the first place the catalyst is ill highly resistant against poisoning so that the feed stoolrs and hydroaenatins gases employed need not be particularly pure. The catalyst therefore retains its activity ior practically unlimited periods without requiring renewal or'regeneration. Moreover very high throughputs can be employed, and in particular as the process is usually carried out under rather high pressure the capacityoi production of a given reaction space is very hiah. Furthermore substanlid tially only saturation oi the polymers occurs but no substantial cracg thereof.

The following examples will further illustrate how the invention may be carried out in practice, but it should he understood that the invendd tion is not limited to the said examples. ,The percentaaes are by weight unless otherwise stated.

Example 1 Di-isobutene is passed together with 5 cubic it metres oi hydrogen per kilogram oi initial material at 215 C. and under a pressure of 250 atmospheres over a catalyst consistina of 2 molecular proportions of tsten disulphide and 1 molecular proportion oi nichelous sulphide, a 3d throughput oi l kilogram. of di-lsobutene per litrc of reaction space per hour being maintained. in this way, practically pure iso-octane is produced besides only 0.5 per cent of gaseous hydrocarbons. The brominenumher of the product 4,0 is 0.2.

if under the same conditions tungsten disulphide is employed as a catalyst, 8 per cent of gaseous hydrocarbons are produced.

Again, if a catalyst is employed consisting of 45 a mixture of 2 molecular proportions of molybdenum disulphide and 1 molecular proportion of copper sulphide, at 215 C. and under a pressure of 250 atmospheres even with a throughput of only 0.5 kilogram of initial material per litre of 60 reaction spaceper hour, a product is obtained,

the bromine number of which is more than 3.

Ii? in this catalyst mixture silver sulphide is substituted for copper sulphide, similar results are obtained. 7 55 A catalyst prepared from chromium hydroxide Example 2 A crude fraction of tri-isobutene is passed with a throughput of 0.8 kilogram per litre of reaction space per hour together with 5 cubic metres of hydrogen per kilogram of initial material at 235 C. and under a pressure 01 250 atmospheres over a catalyst consisting of 2 molecular proportions of tungsten disulphide and 1 molecular proportion of nickelous sulphide. A hydrogenation product is thus obtained with a bromine number of 0.4.

What we claim is:

1. 'A process for the saturation by hydrogenation of liquid olefin polymers boili'ng within the boiling range of gasoline, which comprises hydrogenating them in contact with catalysts substantially free of halides and oi. materials having appreciable cracking action under the conditions ,I 9 Y of treatment and which contain at least one compound selected from the group consisting the sulfides oi molybdenum and tungsten to' gether with at least one compound selected irom the group consisting of the sulfides of nickel and cobalt, whereby the said polymers are saturated with no substantial cracking thereof.

2. In the process as claimed in claim 1, working in contact with a catalyst which contains between 7 and 3 molecular proportions of said first compound and between 3 and 7 molecular proportions of said second compound.

3. In the process as claimed in claim l,' working in contact with a catalyst consisting of tungsten disulphide and nickelous sulphide.

4. In the process as claimed in claim 1, working at temperatures between 175 and 275 C.

5. In the process as claimed in claim 1, work- .ing with an excess of hydrogen under a pressure of at least 50 atmospheres.

- PAUL HEROID.

WALTER KROENIG. HERMANN KAUFMANN. ERNST DONATE. 

